Transition-metal-catalyzed domino reactions of strained bicyclic alkenes

• Austin Pounder,
• Eric Neufeld,
• Peter Myler and
• William Tam

Beilstein J. Org. Chem. 2023, 19, 487–540, doi:10.3762/bjoc.19.38

• catalysts, iron is bringing a renaissance to the idea of sustainable, green catalysis. In 2011, Ito et al. reported a diastereoselective Fe-catalyzed carbozincation of heterobicyclic alkenes 1 with diphenylzinc (74a) (Scheme 13) [47]. Using an ortho-phenylene diphosphine ligand L3, the authors were able to

• . While broadly successful, strongly electron-withdrawing groups lowered the yield of the reaction. In 2021, Isozaki and Nakamura reinvestigated the reaction and established an asymmetric variant of the Fe-catalyzed carbozincation of azabicyclic alkenes 77 (Scheme 13) [48]. Using (S,S)-chiraphos, the

Cobalt- and rhodium-catalyzed carboxylation using carbon dioxide as the C1 source

• Tetsuaki Fujihara and
• Yasushi Tsuji

Beilstein J. Org. Chem. 2018, 14, 2435–2460, doi:10.3762/bjoc.14.221

• useful methods such as the transition-metal-catalyzed carbozincation of alkynes that affords stereodefined alkenylzinc compounds have been developed. To date, a variety of organozinc reagents (RZnX and R2Zn: R = aryl, alkyl, alkenyl, alkynyl, allyl, and benzyl groups) have been used in these reactions

Recent advances in transition-metal-catalyzed intermolecular carbomagnesiation and carbozincation

• Kei Murakami and
• Hideki Yorimitsu

Beilstein J. Org. Chem. 2013, 9, 278–302, doi:10.3762/bjoc.9.34

• Kei Murakami Hideki Yorimitsu Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan Japan Science and Technology Agency, Department of Research Projects (ACT-C), Tokyo 102-0076, Japan 10.3762/bjoc.9.34 Abstract Carbomagnesiation and carbozincation

• involving wide varieties of substrates and reagents. Recent advances of transition-metal-catalyzed carbomagnesiation and carbozincation reactions are reviewed in this article. The contents are separated into five sections: carbomagnesiation and carbozincation of (1) alkynes bearing an electron-withdrawing

• group; (2) alkynes bearing a directing group; (3) strained cyclopropenes; (4) unactivated alkynes or alkenes; and (5) substrates that have two carbon–carbon unsaturated bonds (allenes, dienes, enynes, or diynes). Keywords: alkene; alkyne; carbomagnesiation; carbometalation; carbozincation; transition

Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs

• Fabrice Chemla,
• Florian Dulong,
• Franck Ferreira and
• Alejandro Pérez-Luna

Beilstein J. Org. Chem. 2013, 9, 236–245, doi:10.3762/bjoc.9.28

• 1,4-addition/carbozincation of dialkylzincs or alkyl iodides based on zinc atom radical transfer, in the presence of dimethylzinc with β-(propargyloxy)enoates having pendant iodo- and bromoalkynes, is disclosed. Formation of the carbenoid intermediate is fully stereoselective at −30 °C and arises from

• a formal anti-selective carbozincation reaction. Upon warming, the zinc carbenoid is stereochemically labile and isomerizes to its more stable form. Keywords: carbenoids; carbometallation; carbozincation; radicals; tandem reaction; Introduction The last few years have witnessed a gaining interest

• –carbon double and triple bonds, such reactivity has been advantageously employed in the context of carbozincation chemistry [31]. The intramolecular carbozincation of unactivated terminal alkenes following zinc atom transfer processes, including a 5-exo-trig cyclization step, has been reported. This is

Intramolecular carbolithiation of N-allyl-ynamides: an efficient entry to 1,4-dihydropyridines and pyridines – application to a formal synthesis of sarizotan

• Wafa Gati,
• Mohamed M. Rammah,
• Mohamed B. Rammah and
• Gwilherm Evano

Beilstein J. Org. Chem. 2012, 8, 2214–2222, doi:10.3762/bjoc.8.250

• interest in the chemistry of ynamides [7][8][9][10][11][12][13][14][15][16][17][18] and inspired by recent reports from Meyer and Cossy [19][20][21], Marek [22][23][24] and Lam [25][26] on their carbopalladation, carbocupration and carbozincation, respectively, we decided to study the intramolecular

Recent advances in carbocupration of α-heterosubstituted alkynes

• Ahmad Basheer and
• Ilan Marek

Beilstein J. Org. Chem. 2010, 6, No. 77, doi:10.3762/bjoc.6.77

• adduct 29. However, the reaction was not completely stereoselective (Scheme 13) [25]. Although not a copper-mediated transformation, the rhodium-catalyzed carbozincation of ynamides should be noted since the regioselectivities were, in general, high (>19:1), though in some cases somewhat diminished with

• FG-R2ZnX in the presence of a catalytic amount of CuI (2 mol %), 1-alkynyl sulfoxide 35 undergoes carbozincation to give the functionalized vinylic sulfoxide (Z)-37 in excellent yield. The reaction proceeds in a syn-selective fashion to give only the linear isomer (Scheme 19) [44][45]. The fact that

• Grignard from which the organocopper compound was prepared (Scheme 20) [46][47][48][49][50]. Excess of copper salt provides a better stereoisomeric ratio (>90%) [46]. Only the addition of t-BuCu gave a single stereoisomer [51]. In contrast, the copper-catalyzed carbozincation reaction led to a single